Process for finishing textile materials with a polymer of a vinyl compound and the reaction product of a polyol and an organic polyisocyanate

ABSTRACT

Textile materials which have been treated with an aqueous liquor containing a polymer of a vinyl compound and the reaction product of excess organic polyisocyanate with a polyol. The textile materials have improved crease resistance.

VINYL COMPOUND AND THE REACTION PRODUCT OF A POLYOL AND AN ORGANICPOLYISOCYANATE Inventors: Walter Wunder, Cologne-Flittard; WolfgangKlebert, Leverkusen; Heinz Herlinger, Cologne-Flittard; Karl Schafer,

Opladen, all of Germany I Farbenfabriken Bayer Ak tiengesellschalt,Leverkusen, Germany Filed: July 18, 1968 Appl.No.: 750,999

Related US. Application Data Assignee:

United States Patent 1 3,639,157 Wander et a1. Feb. 1, 1972 [54] PROCESSFOR FINISHING TEXTILE [51] 1nt.C|. ..C08j 1/44,C10m

MATERIALS WITH A POLYMER OF A [58] Field oisearch ..1l7/139.4, 139.5 R,141, 143 R,

117/145, 161 KP, 161 UC, 161 UT; 260/29.6 R, 29.6 H, 29.6 HN, 86.1 N,859; 8/1162, 127.6

Primary Examiner-Murray Katz Assistant ExaminerTheod0re G. DavisAttorney-Plumley, Tyner & Sandt Continuation of Ser. No. 438,102, Mar.8, 1965, abandoned.

117/143 A,117/145,11 7/161U,11 7/ 161 R, 260/29.6 R, zen/29.6 MN

[ ABSTRACT Textile materials which have been treated with an aqueousliquor containing a polymer of a vinyl compound and the reaction productof excess organic polyisocyanate with a polyol, The textile materialshave improved crease resistance.

10 Claims, No Drawings PROCESS FOR FINISHING TEXTILE MATERIALS WITH APOLYMER OF A VINYL COMPOUND AND THE REACTION PRODUCT OF A POLYOL AND ANORGANIC POLYISOCYANATE Thisapplication is a continuation of Ser. No.438,102, filed Mar. 8, 1965, and now abandoned.

This invention is concerned with a process for the production offinishes of textile materials and in particular with the production ofurethane finishes of textile materials which have improved properties.

It has been proposed heretofore to coat textiles with both polyester andpolyether urethanes for various purposes including the shrinkproofing ofwool and the like. However, the heretofore known coatings and finisheshave not been entirely satisfactory because the heretofore know textilefinishing process often leads to unsatisfactory tear resistance in thefinished textile material. Furthermore, the heretofore known textilesare often unsatisfactory with respect to crease resistance, abrasionresistance and retention of shape.

It is therefore an object of this invention to provide improved finishedtextile materials. Another object of this invention is to providetextile materials and finishes therefore which have improved tearstrength. A further object of this invention is to provide improvedtextile materials which have improved crease resistance, abrasionresistance and improved ability to retain their shape. Still anotherobject of this invention is to provide a method of finishing textilesand the finished textiles which may be based on cotton, cellulose, wool,silk, polyamides, polyurethane, polyesters, polycarbonate,polyacrylonitn'le, polypropylene and the like.

The foregoing objects and others which will become apparent from thefollowing description are accomplished generally speaking by providingtextile materials which have been finished by treating them withpolymers or copolymers prepared from vinyl monomers as well as reactionproducts which contain isocyanato groups. Therefore, the presentinvention contemplates textile materialswhich are treated with anaqueous liquor which contains polymers or copolymers prepared from vinylor divinyl monomers as well as reaction products containing isocyanatogroups prepared from compounds having at least two hydroxyl groups and amolecular weight of about 500 to about 6,000 and an organicpolyisocyanate.

The present invention therefore contemplates improved textile materialsof natural or synthetic origin which have improved crease resistance,abrasion resistance, and ability to retain their shape. The textilematerial which may be treated in accordance with the present inventionmay be based on cotton, regenerated cellulose, wool, silk, polyamides,polyurethane, polyesters, polycarbonates, polyacrylonitrile,polypropylene and the like. The process of the invention is particularlynoteworthy in that the tear resistance of the textile material treatedaccording to the invention is either unaffected or slightly affected bythe process of the present invention.

Any suitable vinyl or divinyl monomer may be used for incorporation intothe liquor to be applied to the textile material in accordance with thepresent invention including for example ethylene, propylene, vinylchloride, vinyl acetate, vinyl ethers such as vinyl ethyl ether, alsostyrene or divinyl benzene, butadiene, isoprene or chloroprene as wellas alpha, beta-unsaturated carboxylic acids such as acrylic acid andmethacrylic acid and their nitriles, esters and amides, Polymers havinggroups capable of a reaction with isocyanates are generally preferred;these include for instance the polymers or copolymers prepared fromacrylic acid, methacrylic acid, their hydroxyalkyl esters or amides, aswell as the copolymers obtainable when N-methylol-acrylamide,N-methylol-rnethacrylamide or their derivatives prepared by a reactionwith alcohols containing at least one further functional group arecopolymerized with other olefinically unsaturated compounds, forinstance, in accordance with the process of French Pat. No. 1,328,255.

Any suitable polyol preferably having a molecular weight of from about500 to about 6,000 may be used including polyhydric polyalkylene ethers,polyhydric polyesters and the like. Specific examples of polyhydricpolyalkylene ethers are for example, polyethylene glycol-1000,polypropylene glycol- 2000, polybutylene glycol-1500, polyhexyleneglycol-2000 and the like. Specific examples of polyesters are thoseobtainable from dicarboxylic acids such as succinic acid, adipic acid,sebacic acid, maleic acid and the like and polyhydric alcohols such asethylene glycol, diethylene glycol, propylene glycol, 1,4-butane diol,neopentyl glycol, l,l0-decane diol and the like. The most preferredcompounds are those which have a molecular weight within the range offrom about 800 to about 3,500 and whose, hydroxyl number is 30 to 250.The most preferred acids and alcohols are those which have from two tol0 carbon atoms. 7

Any suitable polyisocyanate may be used, but it is preferred to use analiphatic or cycloaliphatic diisocyanate such as, for example,tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexanediisocyanate, 4,4'dicyclohexyl methane diisocyanate, and also 2,4- and2,6-hexahydrotoluylene diisocyanate. Aromatic diisocyanates are alsosuitable, such as p-phenylene diisocyanate and 2,4- or 2,6-toluylenediisocyanate, as well as triisocyanates such as the reaction product ofthe formula (OCN-(Cl-l N[- CONH-(CH NCO] obtainable from 3 mols ofhexamethylene diisocyanate and 1 mol of water.

The preparation of the reaction products with free isocyanate groups isstraightforward. One merely combines an excess of the organic isocyanatebased on the hydroxyl groups of the polyol and allows the mixture toreact. It is preferred to use a slightly, elevated temperature topromote the reaction and the polyols preferably having from two to sixhydroxyl groups while organic diisocyanates are preferred. The productcontaining the free isocyanate groups are then mixed with the polymersor copolymers preferably in the ratio of 0.25 to 4 parts of the vinyl ordivinyl monomers per part of the compound containing free isocyanategroups. This product may then be combined with sufficient water to makean aqueous liquor having 5 to 70 percent by weight of the total polymerincluding the polymers based on the vinyl or divinyl compounds and thosebased on the reaction product which contain isocyanate groups. It isalso possible: to use the isocyanate groups by applying them in the formof the bisulphite addition products.

The treatment of the textile materials with the aqueous liquor can becarried out by impregnating the textile material with the aqueousliquor, for example, by submerging the textile in the aqueous solutionof polymers and then squeezing off until their increase in weightamounts to 60 to lOOperc'ent. The textile materials are thereafterallowed to dry. It is also possible to spray a textile material withaqueous liquor and then dry the textile material. It is preferred tostore the treated material at room temperature of about 20 to 30 C. forseveral days after the treatment.

Any suitable textile material including those of cotton, regeneratedcellulose, wool, silk, nylon, spandex, polyester fibers, polycarbonates,polyacrylonitrile, polypropylene and the like may be used.

As pointed out above, the textile materials are improved particularlywith regard to crease resistance, abrasion resistance and retention ofshape. They may be used for the production ofclothing, various coveringsand the like.

The invention is further illustrated by the following examples in whichparts are by weight unless otherwise specified.

EXAMPLE I A cotton fabric is impregnated with an aqueous liquor whichcontains, per liter, about 200 grams of a 40 percent aqueous dispersionof a copolymer made from about parts of ethyl acrylate and about 15parts of beta-hydroxypropyl methacrylate as well as about 330 parts ofthe emulsion of an reaction product having isocyanate groups describedbelow. The fabric is then squeezed off until its increase in weightamounts to about l percent, and dried at about 80 to 1 10 C. for about 2to 5 minutes.

The resultant finishing effect is evident from the following table whichalso reproduces the corresponding technological data obtained for thesame fabric by means of the known crease-resistance agentdimethylol-ethylene urea.

Finishing with the crease resistance agent dimethylolethylene urea wascarried out in the usual manner by impregnating the fabric with anaqueous liquor containing, per liter, about 100 grams ofdimethylol-ethylene urea as well as about grams of magnesium chloride;the fabric was then squeezed off until its increase in weight amountedto about 100 percent, and heated at about 150 C. for about 5 minutes.

The above-mentioned emulsion of the reaction product containingisocyanate groups was prepared as follows:

About 3,000 grams of a polypropylene glycol having a molecular weight ofabout 2,000, an --OH number of about 55.5 and an acid number 0.5 wereheated with about 535 grams of hexamethylene diisocyanate at about 110C. for about 2 hours and thereafter at about 130 to 140 C. for anotherabout l hours. An emulsion was then prepared from about 300 grams of theresultant reaction product, whose content of free isocyanate groupsamounts to about 3.9 percent, about 300 grams of ethyl acetate and about400 grams of water with the addition of about 5 grams of laurylsulphate.

EXAMPLE 2 A cotton fabric is impregnated with an aqueous liquor whichcontains, per liter, about 200 grams of a 40 percent aqueous dispersionof a copolymer made from about 85 parts of butyl acrylate, about 10parts of butadiene and about 5 parts of methacrylic acid amide as wellas about 330 grams of the emulsion of the reaction product havingisocyanate groups described in example 1. The fabric is thereaftersqueezed off until its increase in weight amounts to about l00 percentand dried at about 80 to 100 C. for about 4 minutes.

The advantageous effect obtained on the fabric treated in the mannerdescribed and stored at room temperature for about 5 days are evidentfrom the following table:

EXAMPLE 3 A rayon staple fabric is impregnated with an aqueous liquorwhich contains, per liter, about 200 grams of a 38 percent aqueousdispersion of a copolymer made from about 65 parts of vinyl chloride andabout 35 parts of ethylene as well as about 330 grams of the emulsion ofan reaction product hav ing isocyanate groups described in example I.The fabric is then squeezed off until its increase in weight amounts toabout I00 percent and dried at about to 100 C. for about 4 minutes.

The fabric finish is largely crease resistant. At the same time, itsabrasion resistance has been considerably increased. This is evidentfrom the following table which also specifies the abrasion resistanceresult obtained on a rayon staple fabric treated withdimethylol-ethylene urea by the method described in example 1:

Abrasion resistance according to Schopper Untreated fabric 470 revsFabric treated according to the invention 640 revs Fabric treated withdimethlol-ethylene urea 230 revs EXAMPLE 4 A cotton fabric isimpregnated with an aqueous liquor which contains, per liter, about 200grams of the 40 percent aqueous dispersion of a copolymer described inexample 2 as well as about 330 grams of the emulsion of an reactionproduct having isocyanate groups described below. The fabric is thensqueezed off until its increase in weight amounts to 100 percent, anddried at about 80 to 100 C. for about 4 minutes.

The advantageous effects obtained on the fabric treated in the mannerdescribed and stored at room temperature for about 5 days are evidentfrom the following table:

invention The above-mentioned emulsion of the reaction productcontaining isocyanate groups was prepared as follows:

About 600 grams of a branched polypropylene glycol, which was preparedby the propoxylation of trimethylolpropane and has a molecular weight ofabout 3,000, an OH number of about 56 and an acid number 0.5, wereheated to about C. with about 1 l5 grams of 2,4-toluylene diisocyanatefor about 90 minutes. An emulsion was then prepared from about 300 gramsof the resultant reaction product, whose content of free isocyanategroups amounts to 4.1 percent, about 300 grams of ethyl acetate andabout 400 grams of water with the addition of about 5 grams of laurylsulphate.

EXAMPLE 5 A rayon staple fabric is impregnated with an aqueous liquorwhich contains, per liter, about 200 grams of the 40 percent aqueousdispersion of a copolymer described in example 2 as well as about 330grams of the emulsion of the reaction product having isocyanate groupsdescribed below. The fabric is then squeezed off until its increase inweight amounts of about percent, and dried at about C. for about 5minutes.

The advantageous effects obtained on the fabric treated in the mannerdescribed and stored at roomtemperature for about 5 days are evidentfrom the following table:

Dry creasing Wet creasing angle angle i a b a b Untreated fabric 102 11050 61 Fabric treated according to the 140 157 147 153 invention Theabove-mentioned emulsion of the reaction product containing isocyanategroups was prepared as follows:

About 1,000 grams of a branched polypropylene glycol, which was preparedby the propoxylation of trimethylolpropane and has a molecular weight ofabout 3,750, an OH number of about 45 and an acid number 0.5, wereheated with about 135 grams of hexamethylene-diisocyanate for about 2hours to about 1 C. and subsequently about 1 hour to about 130 C. Anemulsion was then prepared from about 300 grams of the resultantreaction product whose content of free isocyanate groups amounts to 2.9percent, about 300 grams of ethyl acetate and about 400 grams of waterwith the addition of about 5 grams lauryl sulphate.

EXAMPLE 6 A woolen fabric is impregnated with an aqueous liquor whichcontains, per liter, about 200 grams of the aqueous dispersion of acopolymer described in example 2 as well as about 200 grams of theemulsion of a reaction product having isocyanate groups described below.The fabric is then squeezed off until its increase in weight amounts toabout 100 percent and dried at about 1 10 C. for about 10 minutes.

The abrasion resistance (repenning) of the fabric treated in the. mannerdescribed and stored at room temperature for about 4 days amounts toabout 1,020 revolutions, whereas the abrasion resistance of theuntreated fabric amounts only to about 210 revolutions. The woolenfabric does not tend to felting when washed in a boiling soda alkalinesolution; shrinkage is considerably diminished as can be seen from thefollowing table:

Shrinkage a b Untreated woolen fabric 18.7% 12.6% Woolen fabric treatedaccording to the invention 3.1% 12% EXAMPLE 7 Silk crape and silkenknitted fabric are treated in the manner described in example 6.

The advantageous effects obtained on the textile materials thus treatedand stored at room temperature for about 5 days are evident from thefollowing table:

Abrasion resist Dry creasing Wet creasing ance (reangle angle penning)A, Silk crepe a b a b l. Untreated 140 151 82 62 60 revs. 2. Treatedaccording to the invention 164 170 140 146 210 revs.

3. Untreated and washed in a soda alkaline solution 4. Treated accordingto the invention and washed in a soda alkaline solution 143 148 112 13140 revs.

160 165 163 151 220 revs.

4. Treated according to the invention and washed in a soda alkalinesolution 160 EXAMPLE 8 A mixed fabric consisting of about 70 parts ofcotton and about 30 parts of fibers of polyterephthalic acid glycolester are impregnated with an aqueous liquor which contains per literabout 100 grams of the 40 percent aqueous dispersion of a copolymerdescribed in example 2 and about 100 grams of the emulsion of a reactionproduct having isocyanate groups described in example 6. The fabric isthen squeezed off until its increase in weight amounts to about 100percent and dried at about 1 10 C. for about 10 minutes.

The advantageous effects obtained on the fabric treated in the mannerdescribed and stored at room temperature for about 5 days are evidentfrom the following table:

Dry creasing Wet creasing angle angle a b a b l. Untreated 93 108 123 2.Treated according to the invention 143 157 148 150 3. Untreated andwashed in a soda alkaline 92 118 126 131 solution 4. Treated accordingto 150 142 153 141i the invention and washed a soda alkaline solutionFabrics made from fibers of polyterephthalic acid glycol ester orpolycaprolactam or mixed fabrics made from equal parts of fibers ofpolyacrylonitrile and polyterephthalic acid glycol ester are treated inthe same manner.

The advantageous effects obtained on the fabrics thus treated and storedat room temperature for about 5 days are evident from the followingtable:

Abrasion resistance (repcnning) 146 148 530 revs.

1060 revs.

170 170 147 167 530 revs.

140 155 132 142 380 revs.

170 171 152 157 720 revs.

It is to be understood that any other suitable vinyl compound,isocyanato terminated compound, textile material or the like could havebeen used in the foregoing examples provided that the teachings of thisdisclosure are followed since the examples are given for the purpose ofillustration.

Although the invention has been described in considerable detail for thepurpose of illustration, it is to be understood that variations can bemade by those skilled in the art without departing from the spirit ofthe invention and scope of the claims.

What is claimed is:

1. An aqueous composition consisting essentially of water and about to70 percent by weight of a mixture of (a) about 0.25 to about 4 parts byweight of a polymer prepared from a vinyl monomer and containing groupscapable of reacting with isocyanate groups and (b) about 1 part byweight of a free isocyanate group containing reaction product of acompound of molecular weight 5006,000 having at least two hydroxylgroups with a stoichiometric excess of an organic polyisocyanate.

2. The composition of claim 1 wherein the component having at least twohydroxyl groups is a polyhydric polyalkylene ether or a polyhydricpolyester having a molecular weight of 800 to 3,500 and a hydroxylnumber of 30 to 250.

3. The composition of claim 1 wherein the organic polyisocyanate is analiphatic or cycloaliphatic diisocyanate.

4. A method for finishing textile material comprising treating a textilematerial with an aqueous liquor consisting essentially of water andabout 5 to 70 percent by weight of a mixture of (a) about 0.25 to about4 parts by weight of a polymer prepared from a vinyl monomer andcontaining groups capable of reacting with isocyanate groups and (b)about 1 part by weight of a free isocyanate group containing reactionproduct of a compound of molecular weight 5006,000 having at least twohydroxyl groups with a stoichiometric excess of an organicpolyisocyanate, and drying the treated textile material.

5. The method of claim 4 wherein the treated and dried textile materialis submitted to the further step of storage at room temperature.

6. The method of claim 4 I wherein the textile material is selected fromthe group consisting of cotton, regenerated cellulose, wool, silk,polyamide, polyurethane, polyester, polycarbonate, polyacrylonitrile andpolypropylene.

7. The method of claim 4 wherein the drying is accomplished at to C.

8. The textile material prepared by the process of claim 4.

9. A method for finishing textile materials comprising treating atextile material with an aqueous liquor consisting essentially of waterand an amount effective to impart improved physical properties to thetextile material when coated thereon of a mixture of (a) about 0.25 toabout 4 parts by weight of a polymer prepared from a vinyl monomer andcontaining groups capable of reacting with isocyanate groups and (b)about 1 part by weight of a free isocyanate group containing reactionproduct of a compound of molecular weight 500-6,000 having at least twohydroxyl groups with a stoichiometric excess ofan organicpolyisocyanate, and drying the treated textile material.

10. The textile material prepared by the process of claim 9.

2. The composition of claim 1 wherein the component having at least twohydroxyl groups is a polyhydric polyalkylene ether or a polyhydricpolyester having a molecular weight of 800 to 3,500 and a hydroxylnumber of 30 to
 250. 3. The composition of claim 1 wherein the organicpolyisocyanate is an aliphatic or cycloaliphatic diisocyanate.
 4. Amethod for finishing textile material comprising treating a textilematerial with an aqueous liquor consisting essentially of water andabout 5 to 70 percent by weight of a mixture of (a) about 0.25 to about4 parts by weight of a polymer prepared from a vinyl monomer andcontaining groups capable of reacting with isocyanate groups and (b)about 1 part by weight of a free isocyaNate group containing reactionproduct of a compound of molecular weight 500-6,000 having at least twohydroxyl groups with a stoichiometric excess of an organicpolyisocyanate, and drying the treated textile material.
 5. The methodof claim 4 wherein the treated and dried textile material is submittedto the further step of storage at room temperature.
 6. The method ofclaim 4 wherein the textile material is selected from the groupconsisting of cotton, regenerated cellulose, wool, silk, polyamide,polyurethane, polyester, polycarbonate, polyacrylonitrile andpolypropylene.
 7. The method of claim 4 wherein the drying isaccomplished at 80* to 110* C.
 8. The textile material prepared by theprocess of claim
 4. 9. A method for finishing textile materialscomprising treating a textile material with an aqueous liquor consistingessentially of water and an amount effective to impart improved physicalproperties to the textile material when coated thereon of a mixture of(a) about 0.25 to about 4 parts by weight of a polymer prepared from avinyl monomer and containing groups capable of reacting with isocyanategroups and (b) about 1 part by weight of a free isocyanate groupcontaining reaction product of a compound of molecular weight 500-6,000having at least two hydroxyl groups with a stoichiometric excess of anorganic polyisocyanate, and drying the treated textile material.
 10. Thetextile material prepared by the process of claim 9.